Poly silicone rubber

Whilst the Tg of poly(dimethylsiloxane) rubbers is reported to be as low as -123°C they do become stiff at about -60 to -80°C due to some crystallisation. Copolymerisation of the dimethyl intermediate with a small amount of a dichlorodiphenylsilane or, preferably, phenylmethyldichlorosilane, leads to an irregular structure and hence amorphous polymer which thus remains a rubber down to its Tg. Although this is higher than the Tg of the dimethylsiloxane it is lower than the so that the polymer remains rubbery down to a lower temperature (in some cases down to -100°C). The Tg does, however, increase steadily with the fraction of phenylsiloxane and eventually rises above that of the of the dimethylsilicone rubber. In practice the use of about 10% of phenyldichlorosilane is sufficient to inhibit crystallisation without causing an excess rise in the glass transition temperature. As with the polydimethylsilox-anes, most methylphenyl silicone rubbers also contain a small amount of vinyl groups. 

Substantial improvements in the heat-resisting capability of silicone rubbers were achieved with the appearance of the poly(carborane siloxanes). First described in 1966, they were introduced commercially by the Olin Corporation in 1971 as Dexsil. The polymers have the essential structure... 

In the JKR experiments, a macroscopic spherical cap of a soft, elastic material is in contact with a planar surface. In these experiments, the contact radius is measured as a function of the applied load (a versus P) using an optical microscope, and the interfacial adhesion (W) is determined using Eqs. 11 and 16. In their original work, Johnson et al. [6] measured a versus P between a rubber-rubber interface, and the interface between crosslinked silicone rubber sphere and poly(methyl methacrylate) flat. The apparatus used for these measurements was fairly simple. The contact radius was measured using a simple optical microscope. This type of measurement is particularly suitable for soft elastic materials. 

Uses. There are about forty to fifty organic peroxides commercially available in more than seventy formulations designed for specific applications which include (1) initiators for vinyl monomer polymerizations, and copolymerizations of monomers such as vinyl chloride, ethylene, styrene, vinyl acetate, acrylics, fluoroolefms and buta-dienestyrene (2) curing agents for thermoset polyesters, styrenated alkyds and oils, silicone rubbers and poly allyl diglycol carbonates ... 

Lednicky et studied the structure of silicone rubber-hydrogel based on poly(HEMA) by... 

SCHEME 1 Mechanism for chemical modification of poly(dimethysiloxane) (silicone rubber) membranes with ion-sensing active material. 

The design of bioeompatible (blood compatible) potentiometric ion sensors was described in this chapter. Sensing membranes fabricated by crosslinked poly(dimethylsiloxane) (silicone rubber) and sol gel-derived materials are excellent for potentiometric ion sensors. Their sensor membrane properties are comparable to conventional plasticized-PVC membranes, and their thrombogenic properties are superior to the PVC-based membranes. Specifically, membranes modified chemically by neutral carriers and anion excluders are very promising, because the toxicity is alleviated drastically. The sensor properties are still excellent in spite of the chemical bonding of neutral carriers on membranes. 

This process involves the suspension of the biocatalyst in a monomer solution which is polymerized, and the enzymes are entrapped within the polymer lattice during the crosslinking process. This method differs from the covalent binding that the enzyme itself does not bind to the gel matrix. Due to the size of the biomolecule it will not diffuse out of the polymer network but small substrate or product molecules can transfer across or within it to ensure the continuous transformation. For sensing purposes, the polymer matrix can be formed directly on the surface of the fiber, or polymerized onto a transparent support (for instance, glass) that is then coupled to the fiber. The most popular matrices include polyacrylamide (Figure 5), silicone rubber, poly(vinyl alcohol), starch and polyurethane. 

On the other hand, silicones are used in organic composites. The application of alloys composed of the fully cured silicone rubber particles in a continuous thermoplastic phase, called thermoplastic silicone vulcanizate, which offers high-performance materials, has been reported.506,507 Functionalized POSS was not only co-polymerized, but also blended with poly(methylmethacrylate) to study the effect of silsesquioxanes on the thermal stability of thermoplastics.508... 

Cooper et al. [21, 22] reported in detail the results of their laborious work on the adsorption of four proteins human serum albumin (HSA), fibrinogen (FGN), fibronectin (FN), and vitronectin (VN), on five biomaterials polyethylene (PE), silicone rubber (SR), Teflon-FEP (FEP), poly(tetramethylene oxide)-poly-urethane (PTMO-PU), and polyethylene oxide)-polyurethane(PEO-PU). Hard segments of these polyurethanes are composed of a methylene-bis(p-phenylisocyanate) (MDI) chain extended wih 1,4-butanediol. 

X-ray diffraction techniques can be used to establish the structure of crystalline polymers. Measurements are typically made on crystalline lamellar platelets grown from dilute solution, fibres or stretched films. Such methods have been applied to several different inorganic polymers. For example, based on measurements on stretched samples of silicone rubber, poly(dimethylsiloxane) (Me2SiO) has been shown to possess a helical conformation (Figure 8.4). ... 

HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HNS NTO NTO/HMX NTO/HMX NTO/HMX PETN PETN PETN PETN PETN PETN PETN PETN PETN PETN RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX TATB/HMX Cariflex (thermoplastic elastomer) Hydroxy-terminated polybutadiene (polyurethane) Hydroxy-terminated polyester Kraton (block copolymer of styrene and ethylene-butylene) Nylon (polyamide) Polyester resin-styrene Polyethylene Polyurethane Poly(vinyl) alcohol Poly(vinyl) butyral resin Teflon (polytetrafluoroethylene) Viton (fluoroelastomer) Teflon (polytetrafluoroethylene) Cariflex (block copolymer of butadiene-styrene) Cariflex (block copolymer of butadiene-styrene) Estane (polyester polyurethane copolymer) Hytemp (thermoplastic elastomer) Butyl rubber with acetyl tributylcitrate Epoxy resin-diethylenetriamine Kraton (block copolymer of styrene and ethylene-butylene) Latex with bis-(2-ethylhexyl adipate) Nylon (polyamide) Polyester and styrene copolymer Poly(ethyl acrylate) with dibutyl phthalate Silicone rubber Viton (fluoroelastomer) Teflon (polytetrafluoroethylene) Epoxy ether Exon (polychlorotrifluoroethylene/vinylidine chloride) Hydroxy-terminated polybutadiene (polyurethane) Kel-F (polychlorotrifluoroethylene) Nylon (polyamide) Nylon and aluminium Nitro-fluoroalkyl epoxides Polyacrylate and paraffin Polyamide resin Polyisobutylene/Teflon (polytetrafluoroethylene) Polyester Polystyrene Teflon (polytetrafluoroethylene) Kraton (block copolymer of styrene and ethylene-butylene)... 

The authors of the above-discussed results consider the constant rate of heparin elution to be absolutely necessary for a successful functioning of the implant. Catheters made of these copolymers are much better, in respect of their thromboresistant properties, than the commercially available poly(tetrafluoroethylene) polyethylene, and plasticized polyvinyl chloride catheters (Table 8). The tested catheters were clotted in 9 cases of 81 (11 %), whereas usual silicone rubber catheters were clotted in 5 cases of 8 (63 %)70). 

For instance, the modification of silicone rubbers, poly-(tetrafluoroethylene), polyethylene, and segmented polyurethanes by ionic attachment of heparin was shown to result in a decrease of platelet adhesion onto these polymers71 74 75. A similar... 

The First plastic sabots were made of glass-fiber filled diallylphthalate sheathed in nylon and they included metal reinforcements whenever it was felt necessary to redistribute the stresses. The nylon sheath was necessitated by the abrasive nature of glass-filled materials. Nylon also is used for rotating bands on projectiles and on metal sabots. Other plastics used for the structural portions of sabots include poly propylenes, polycarbonates, celluloses, epoxies and phenolics. Polyethylene, neoprene, and silicone rubbers are used for seals and obturators... 

In any membrane process, it is desirable for the minor components to permeate the membrane, so the acetone-selective silicone rubber membrane is best used to treat dilute acetone feed streams, concentrating most of the acetone in a small volume of permeate. The water-selective poly(vinyl alcohol) membrane is best used to treat concentrated acetone feed streams, concentrating most of the water in a small volume of permeate. Both membranes are more selective than distillation, which relies on the vapor-liquid equilibrium to achieve separation. 

Figure 9.5 Pervaporation separation of acetone-water mixtures achieved with a water-selective membrane poly(vinyl alcohol) (PVA), and an acetone-selective membrane (silicone rubber) [21]. Reprinted from Hollein et al. [21], p. 1051 by courtesy of Marcel Dekker, Inc.

Yet another approach to stabilizing facilitated transport membranes is to form multilayer structures in which the supported liquid-selective membrane is encapsulated between thin layers of very permeable but nonselective dense polymer layers. The coating layers must be very permeable to avoid reducing the gas flux through the membrane materials such as silicone rubber or poly(trimethylsilox-ane) are usually used [26],... 

Bessarabov s devices use composite membranes consisting of a thin silicone rubber polymer layer coated onto a microporous poly(vinylidene fluoride) support layer. These membranes have high fluxes and minimal selectivities for the hydrocarbon gases, but the dense silicone layer provides a more positive barrier to bleed-through of liquid than do capillary effects with simple micro-porous membranes. 

In contrast, organophilic PV membranes are used for removal of (volatile) organic compounds from aqueous solutions. They are typically made of rubbery polymers (elastomers). Cross-linked silicone rubber (PDMS) is the state-of-the-art for the selective barrier [1, 43, 44]. Nevertheless, glassy polymers (e.g., substituted polyacetylene or poly(l-(trimethylsilyl)-l-propyne, PTMSP) were also observed to be preferentially permeable for organics from water. Polyether-polyamide block-copolymers, combining permeable hydrophilic and stabilizing hydrophobic domains within one material, are also successfully used as a selective barrier. 

Table 4.2 illustrates the various selectivity factors for some typical rubbery polymers, that is, silicone rubber, poly(dimethyl siloxane), and natural rubber, polyiso-prene, and a glassy polymer, polysulfone. Here, we consider the important 02/N2 pair and several pairs involving C02 that will be our focus later. In all the cases, the solubility selectivity is greater than unity and there is not a large difference between rubbery and glassy polymers. For most of these pairs, the diffusion selectivity is greater than unity, but there are some exceptions for C02/02 and C02/N2 that reflect... 

Yang, J.S. and Hsiue, G.H. (1997) Selective olefin permeation through Ag(I) contained silicone rubber-graft-poly(acrylic acid) membranes. Journal of Membrane Science, 126, 139. 

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